Combined cracking and selective hydrogen combustion for catalytic cracking

ABSTRACT

A catalyst system and process for combined cracking and selective hydrogen combustion of hydrocarbons are disclosed. The catalyst comprises (1) at least one solid acid component, (2) at least one metal-based component comprised of two or more elements from Groups 4-15 of the Periodic Table of the Elements and at least one of oxygen and sulfur, wherein the elements from Groups 4-15 and the at least one of oxygen and sulfur are chemically bound both within and between the groups and (3) at least one of at least one support, at least one filler and at least one binder. The process is such that the yield of hydrogen is less than the yield of hydrogen when contacting the hydrocarbons with the solid acid component alone.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a novel catalyst composition andits use in a novel hydrocarbons cracking process. The catalyst isparticularly useful in reducing the concentration of hydrogen incracking products.

[0003] 2. Discussion of Background Information

[0004] Current cracking technologies for the production of light olefins(e.g. ethylene, propylene and, optionally, butylenes), gasoline andother cracked products such as light paraffins and naphtha can beclassified into the two categories of thermal cracking (also known assteam cracking) and catalytic cracking. While these technologies havebeen practiced for many years and are considered the workhorses forlight-olefin production, both have disadvantages.

[0005] Steam or thermal cracking, a robust technology that does notutilize catalyst, produces the more valuable ethylene as the primarylight olefin product. It is particularly suitable for crackingparaffinic feedstocks to a wide range of products including hydrogen,light olefins, light paraffins, and heavier liquid hydrocarbon productssuch as pyrolysis gasoline, steam cracked gas oil, etc. However, steamcracking is an expensive, complex technology due to required specialconstruction material to sustain high cracking temperatures (˜850° C.)and high energy input. Sulfur addition is required to passivate thefurnace metal surfaces on a continuous basis, creating such undesirableside effects as environmental and product contamination. Steam crackingis not considered to be suitable for cracking feeds containing highconcentrations of light olefins as it makes high levels of low valueheavy by-products due to the more reactive nature of the olefin feeds.In addition, steam cracking makes a relatively low amount of propylene,and, therefore, is not considered suitable for meeting the anticipatedgrowing demand for propylene in the future. Also, steam crackingrequires steam dilution to control product selectivity and to maintainan acceptable run length; steam dilution is costly in terms of capitalinvestment and energy consumption.

[0006] Current catalytic cracking technologies employ solid acidcatalysts such as zeolites to promote cracking reactions. Unlike steamcracking technology, propylene is the primary light olefin product ofcatalytic cracking. Accordingly, catalytic cracking would be consideredas the main source for growing propylene demand. Catalytic cracking canbe classified into the following two general categories. The firstcategory is Fluid Catalytic Cracking (FCC), which is the preferredrefining process for converting higher boiling petroleum fractions intolower boiling products, such as gasoline, cracked naphtha and lightolefins. The FCC catalyst of fine particles acts like a fluid andcirculates in a closed cycle between a cracking reactor and a separateregenerator. In general, FCC catalysts can be classified into twocategories—FCC base catalysts and FCC additive catalysts. Typical FCCcatalysts contain the base catalysts which comprise a zeolite componentand a matrix component. The zeolite is a major contributor for thecatalyst activity, selectivity and stability. Examples of the zeolitecomponent include Y zeolite and beta zeolite. The zeolite usually istreated with various modifications such as dealumination, rare earthexchange, phosphorous treatment, etc. Examples of typical matrixmaterials include amorphous compounds such as silica, alumina,silica-alumina, silica-magnesia, and clays such as kaolinite, halloysiteor montmorillonite. The matrix component can serve several purposes. Itcan be used to bind the zeolite component to form catalyst particles. Itcan serve as a diffusion medium for the transport of feed and productmolecules. It also can act as a filler which dilutes the zeoliteparticles to moderate the catalyst activity. In addition, the matrix canhelp heat transfer.

[0007] Some FCC catalysts also contain FCC additive catalyst(s),including, by way of non-limiting examples, octane-boosting additive,metal passivation additives, SOx reduction additives, NOx reductionadditives, CO oxidation additives, coke oxidation additives, etc. Theadditive catalyst(s) can be either incorporated into the base catalystmatrix or used as separate catalyst particles. When used as separatecatalyst particles, the additive catalyst(s)will contain in addition tothe catalytic active components their own matrix materials, which may ormay not be the same as the base catalyst matrix. Examples (U.S. Pat. No.4,368,114, which is incorporated herein by reference in its entirety) ofthe main catalytic components for octane-boosting additive catalystsinclude ZSM-5 zeolite, ZSM-11 zeolite, beta zeolite, etc. Examples ofSOx reduction additives include magnesia, ceria-alumina, rare earths onalumina, etc. Examples of CO oxidation additives include platinum and/orpalladium either directly added to the base catalyst at trace levels ordispersed on a support such as alumina or silica alumina (U.S. Pat. Nos.4,072,600 and 4,107,032, which are incorporated herein by reference intheir entirety). Non-limiting examples of coke oxidation promotersinclude lanthanum and iron embedded in the base catalyst (U.S. Pat. No.4,137,151, which is incorporated herein by reference in its entirety).Examples of metal passivation additives include barium titanium oxide(U.S. Pat. No. 4,810,358, which is incorporated herein by reference inits entirety), calcium-containing additives selected from the groupconsisting of calcium-titanium, calcium-zirconium,calcium-titanium-zirconium oxides and mixtures thereof (U.S. Pat. No.4,451,355, which is incorporated herein by reference in its entirety),and antimony and/or tin on magnesium-containing clays (U.S. Pat. No.4,466,884, which is incorporated herein by reference in its entirety).

[0008] For a riser FCC unit, fresh feed contacts hot catalyst from theregenerator at the base of the riser reactor. The cracked products aredischarged from the riser to pass through a main column, which producesseveral liquid streams and a vapor stream containing hydrogen, methane,ethane, propane, butane, and light olefins. The vapor stream iscompressed in a wet gas compressor and charged to the unsaturated gasfacility for product purification. Another technology in this categoryis moving bed cracking or Thermoform Catalytic Cracking (TCC). The TCCcatalyst is in the form of small beads, which circulate between areactor and a regenerator in the form of a moving bed. A furtherdescription of the FCC process may be found in the monograph, “FluidCatalytic Cracking with Zeolite Catalysts,” P. B. Venuto and E. T.Habib, Marcel Dekker, New York, 1978, incorporated by reference.

[0009] The second category of catalytic cracking is catalytic crackingof naphtha, the main purpose of which is the generation of lightolefins. Either FCC-type reactor/regenerator technology (U.S. Pat. No.5,043,522, which is incorporated herein by reference in its entirety),or fixed-bed reactor technology (EP0921175A1 and EP0921179A1, which areincorporated herein by reference in their entirety), can be used. Theproducts, which include liquid streams and a vapor stream of hydrogen,methane, ethane, propane, butane, and light olefins go through a seriesof treatments similar to that for the FCC products.

[0010] As pointed out above, current cracking technologies typicallyproduce vapor streams containing mixtures of hydrogen, light paraffins(e. g. methane, ethane, propane, and optionally, butanes) and lightolefins. In some cases, such as ethane cracking, hydrogen is recoveredin high purity as a valued product. In many other cases, such as steamcracking of naphtha, FCC of gas oil, catalytic cracking of olefinicnaphtha, etc., hydrogen is undesirable due to the difficulty ofseparating H₂ from the light olefins (ethylene and propylene). Thepresence of even a moderate quantity of H₂ in cracked productsnecessitates such expensive equipment as multi-stage gas compressors andcomplex chill trains, which contribute significantly to the cost ofolefin production. If cracked products could be produced with minimal orno hydrogen in the reactor effluent, a significant cost saving could berealized for grassroots plants and for debottlenecking existing plants,and lower olefin manufacturing cost could be realized.

[0011] Conventional approaches to deal with the hydrogen issue havefocused on post-reactor separation. That is, attempts have been made touse various reaction and/or separation techniques such as pressure swingadsorption or membranes to remove hydrogen from the olefins. However,these technologies suffer from a few disadvantages. First, they mostlyoperate at relatively high pressure (>7 atmospheres), which does nothelp reduce the burden on the compressors. Second, these technologiesare expensive. Third, their performance of separating the olefin productinto a H₂-rich stream and a H₂-poor stream is often unsatisfactory. Atypical problem has been the loss of olefins to the hydrogen-rich streamdue to an incomplete separation. As a result, many commercial plantsstill employ the complex and costly high-pressure cryogenic separation.

[0012] U.S. Pat. No. 4,497,971, which is incorporated herein byreference in its entirety, relates to an improved catalytic process forthe cracking and oxidative dehydrogenation of light paraffins, and acatalyst therefor. According to this patent, a paraffin or mixtures ofparaffins having from 2 to 5 carbon atoms is oxidatively dehydrogenatedin the presence of a cobalt-based catalyst composition which not onlyhas oxidative dehydrogenation capabilities but also has the capabilityto crack paraffins having more than two carbon atoms so that a paraffinsuch as propane can be converted to ethylene. If the feed to theoxidative dehydrogenation process contains paraffins having more thantwo carbon atoms, some cracking of such paraffins will occur at theconditions at which the oxidative dehydrogenation process is carriedout.

[0013] U.S. Pat. No. 4,781,816, which is incorporated herein byreference in its entirety, relates to a catalytic cracking process andto a process for cracking heavy oils. It is an object of the disclosedinvention to provide a process for cracking hydrocarbon-containingfeedstocks, which contain vanadium compounds as impurities. According tothis patent, the feedstream to be treated contains at least about 5 wppmvanadium. The catalyst comprises a physical mixture of zeolite embeddedin an inorganic refractory matrix material, and at least one oxide of ametal selected from the group consisting of Be, Mg, Ca, Sr, Ba and La(preferably MgO) on a support material comprising silica.

[0014] U.S. Pat. No. 5,002,653, which is incorporated herein byreference in its entirety, relates to an improved catalytic crackingprocess using a catalyst composition for use in the conversion ofhydrocarbons to lower-boiling fractions. More particularly, theinvention comprises a process for using a dual component catalyst systemfor fluid catalytic cracking, which catalyst demonstrates vanadiumpassivation and improved sulfur tolerance. The catalyst comprises afirst component comprising a cracking catalyst having high activity,and, a second component, as a separate and distinct entity, the secondcomponent comprising a calcium/magnesium-containing material incombination with a magnesium-containing material, wherein thecalcium/magnesium-containing compound is active for metals trapping,especially vanadium trapping.

[0015] U.S. Pat. No. 5,527,979, which is incorporated herein byreference in its entirety, relates to a catalytic oxidativedehydrogenation process for alkane molecules having 2-5 carbon atoms. Itis an object of the disclosed invention to provide a process fordehydrogenation of alkanes to alkenes. More particularly, the inventioncomprises a process of at least two reactors in series, in which analkane feed is dehydrogenated to produce alkene and hydrogen over anequilibrium dehydrogenation catalyst in a first reactor, and theeffluent from the first reactor, along with oxygen, is passed into asecond reactor containing a metal oxide catalyst which serves toselectively catalyze the combustion of hydrogen. At least a portion ofthe effluent from the second reactor is contacted with a solid materialcomprising a dehydrogenation catalyst to further convert unreactedalkane to additional quantities of alkene and hydrogen. The equilibriumdehydrogenation catalyst comprises at least one metal from Cr, Mo, Ga,Zn and a metal from Groups 8-10. The metal oxide catalyst comprises anoxide of at least one metal from the group of Bi, In, Sb, Zn, Tl, Pb andTe.

[0016] U.S. Pat. No. 5,530,171, which is incorporated herein byreference in its entirety, relates to a catalytic oxidativedehydrogenation process for alkane molecules having 2-5 carbon atoms. Itis an object of the disclosed invention to provide a process fordehydrogenation of alkanes to alkenes. More particularly, the inventioncomprises a process of simultaneous equilibrium dehydrogenation ofalkanes to alkenes and combustion of the hydrogen formed to drive theequilibrium dehydrogenation reaction further to the product alkenes. Theprocess involves passing the alkane feed into a reactor containing bothan equilibrium dehydrogenation catalyst and a reducible metal oxide,whereby the alkane is dehydrogenated and the hydrogen produced issimulataneously and selectively combusted in oxidation/reductionreaction with the reducible metal oxide. The process further comprisesinterrupting the flow of alkane into the reaction zone, reacting thereduced metal oxide with a source of oxygen to regenerate the originaloxidized form of the reducible metal oxide, and resuming the reaction inthe reaction zone using the regenerated from of the reducible metaloxide. The dehydrogenation catalyst comprises Pt or Pd, and thereducible metal oxide is an oxide of at least one metal from the groupof Bi, In, Sb, Zn, Tl, Pb and Te.

[0017] U.S. Pat. No. 5,550,309, which is incorporated herein byreference in its entirety, relates to a catalytic dehydrogenationprocess for a hydrocarbon or oxygenated hydrocarbon feed. Moreparticularly, the invention comprises a process of contacting the feedwith a catalyst bed comprising a dehydrogenation catalyst and a porouscoated hydrogen retention agent in which the dehydrogenation catalystproduces a product stream of a dehydrogenated product and hydrogen andthe porous coated hydrogen retention agent selectively removes, adsorbsor react with some of the hydrogen from the product stream, removing thereaction products from the reaction chamber, removing the adsorbedhydrogen from the hydrogen retention agent or oxidizing the reducedhydrogen retention agent to regenerate the hydrogen retention agent, andusing the regenerated hydrogen retention agent for reaction with feed.

[0018] U.S. Pat. No. 4,466,884, which is incorporated herein byreference in its entirety, relates to a catalytic cracking process forfeedstocks having high metals content such as vanadium, nickel, iron andcopper. More particularly, the invention comprises a process ofcontacting the feed with a catalyst composition comprising a solidcracking catalyst and a diluent containing antimony and/or tin. Thesolid cracking catalyst is to provide good cracking activity. Thediluent can be compound or compounds having little activity such asmagnesium compounds, titanium compounds, etc. The function of theantimony and/or tin in the diluent is to react with the nickel orvanadium in the feedstocks to form inert compounds thereby reducing thedeactivating effects of nickel and vanadium on the solid crackingcatalyst.

[0019] U.S. Pat. No. 4,451,355, which is incorporated herein byreference in its entirety, relates to a hydrocarbon conversion processfor feedstocks having a significant concentration of vanadium. Moreparticularly, the invention comprises a process of contacting the feedhaving a significant concentration of vanadium with a cracking catalystcontaining a calcium containing additive selected from the groupconsisting of calcium-titanium, calcium-zirconium,calcium-titanium-zirconium oxides and mixtures thereof. A preferredcalcium additive is a calcium titanate perovskite (CaTiO3) or calciumzirconate (CaZrO3) perovskite. It is theorized that addition of thecalcium-containing additive prevents the detrimental vanadiuminteraction with the zeolite in the cracking catalyst by acting as asink for vanadium.

[0020] A significant need exists for a cracking technology thatovercomes the previously discussed disadvantages of present, commercialcracking technology due to of the presence of hydrogen in crackedproducts.

SUMMARY OF THE INVENTION

[0021] One aspect of the present invention relates to a catalyst systemcomprising (1) at least one solid acid component, (2) at least onemetal-based component comprised of two or more elements from Groups 4-15of the Periodic Table of the Elements and at least one of oxygen andsulfur, wherein the elements from Groups 4-15 and the at least one ofoxygen and sulfur are chemically bound both within and between thegroups and (3) at least one of at least one support, at least one fillerand at least one binder.

[0022] The solid acid component can comprise at least one of at leastone support, at least one filler and at least one binder. In anotheraspect, the solid acid component can comprise at least one of one ormore amorphous solid acids, one or more crystalline solid acids and oneor more supported acids. In one embodiment of the present invention, thesolid acid catalyst comprises at least one molecular sieve. In apreferred embodiment, the molecular sieve comprises at least one ofcrystalline silicates, crystalline substituted silicates, crystallinealuminosilicates, crystalline substituted aluminosilicates, crystallinealuminophosphates, crystalline substituted aluminophosphates,zeolite-bound-zeolite, having 8- or greater-than-8 membered oxygen ringsin framework structures. In another embodiment of the present invention,the solid acid component is at least one zeolite. The zeolite cancomprise at least one of faujasite and MFI. The faujasite zeolite can beY zeolite or modified Y zeolites such as dealuminated Y zeolite, highsilica Y zeolite, rare earth-exchanged Y zeolite, etc. The MFI zeolitecan be ZSM-5 zeolite or modified ZSM-5 zeolites such as phosphroustreated ZSM-5 zeolite and lanthanum treated ZSM-5 zeolite. In anotherembodiment of the present invention, the solid acid component can alsobe conventional FCC catalysts including catalysts containing zeolite Y,modified zeolite Y, Zeolite beta, and mixtures thereof, and catalystscontaining a mixture of zeolite Y and a medium-pore, shape-selectivemolecular sieve species such as ZSM-5, or a mixture of an amorphousacidic material and ZSM-5. Such catalysts are described in U.S. Pat. No.No. 5,318,692, incorporated by reference herein.

[0023] In a further aspect of the present invention, the metal-basedcomponent comprises at least one perovskite crystal structure.Furthermore, the metal-based component can comprise at least one of atleast one support, at least one filler and at least one binder.

[0024] In another aspect of the present invention, preferably, theelements from Groups 4-15 are at least two of titanium, vanadium,chromium, manganese, iron, cobalt, nickel, copper, zinc, boron,aluminum, phosphorous, gallium, germanium, zirconium, niobium,molybdenum, ruthenium, rhodium, palladium, silver, indium, tin,antimony, hafnium, tungsten, rhenium, iridium, platinum, gold, lead andbismuth.

[0025] In another aspect of the invention, the oxygen is preferred.

[0026] The weight ratio of solid acid component to the total weight ofthe metal-based component can be about 1000:1 to 1:1000. Preferably,this ratio is about 500:1 to 1:500. Mostpreferably, this ratio is about100:1 to 1:100.

[0027] According to another aspect of the present invention, a processcomprises simultaneously contacting a hydrocarbon feedstream undercracking conditions with a catalyst system comprising (1) at least onesolid acid component, (2) at least one metal-based component comprisedof two or more elements from Groups 4-15 of the Periodic Table of theElements and at least one of oxygen and sulfur, wherein the elementsfrom Groups 4-15 and the at least one of oxygen and sulfur arechemically bound both within and between the groups and (3) at least oneof at least one support, at least one filler and at least one binder.

[0028] It is believed that the inventive catalyst system is unique inthat, among other things, it permits simultaneous catalytic cracking ofhydrocarbon feedstreams to cracked products and combustion of resultanthydrogen to water. Preferably, the hydrogen combustion comprisesselective hydrogen combustion. The selective hydrogen combustion can beanaerobic without the feeding of free-oxygen containing gas to thereaction, or it can be conducted with the feeding of free-oxygencontaining gas.

[0029] Preferably, the yield of hydrogen is less than the yield ofhydrogen when contacting said hydrocarbon feedstream(s) with said solidacid component alone under said catalytic reaction conditions.Preferably, the yield of hydrogen is at least 10% less than the yield ofhydrogen when contacting said hydrocarbon feedstream(s) with said solidacid component alone under catalytic reaction conditions. Morepreferably, the yield of hydrogen is at least 25% less, more preferablyat 50% less, even more preferably at least 75%, more preferably, atleast 90%, and most preferably greater than 99% less than the yield ofhydrogen when contacting said hydrocarbon feedstream(s) with said solidacid component alone under catalytic reaction conditions.

[0030] In a further aspect of the present invention, a catalyticcracking process comprises

[0031] (A) charging at least one hydrocarbon feedstream to a fluidcatalytic cracking reactor,

[0032] (B) charging a hot fluidized cracking/selective hydrogencombustion catalyst system from a catalyst regenerator to said fluidcatalytic cracking reactor, said catalyst system comprising: (1) atleast one solid acid component, (2) at least one metal-based componentcomprised of two or more elements from Groups 4-15 of the Periodic Tableof the Elements and at least one of oxygen and sulfur, wherein theelements from Groups 4-15 and the at least one of oxygen and sulfur arechemically bound both within and between the groups and (3) at least oneof at least one support, at least one filler and at least one binder;

[0033] (C) catalytically cracking said feedstream(s) and combustingresultant hydrogen at 300-800° C. to produce a stream of crackedproducts and uncracked feed and a spent catalyst system comprising saidfluid catalytic cracking catalyst and said selective hydrogen combustioncatalyst which are discharged from said reactor,

[0034] (D) separating a phase rich in said cracked products anduncracked feed from a phase rich in said spent catalyst system,

[0035] (E) stripping said spent catalyst system at stripping conditionsto produce a stripped catalyst phase,

[0036] (F) decoking and oxidizing said stripped catalyst phase in acatalyst regenerator at catalyst regeneration conditions to produce saidhot fluidized cracking/selective hydrogen combustion catalyst system,which is recycled to the said reactor, and

[0037] (G) separating and recovering said cracked products and uncrackedfeed.

[0038] Another aspect of the present invention relates to a processcomprising contacting at least one hydrocarbon feedstream with acracking/selective hydrogen combustion catalyst system under effectivecatalytic reaction conditions to produce cracked products and uncrackedfeed comprising liquid and gaseous hydrocarbons, wherein the yield ofhydrogen is less than the yield of hydrogen when contacting saidhydrocarbon feedstream(s) with said cracking catalyst alone under saidcatalytic reaction conditions. Preferably, the yield of hydrogen is atleast 10% less than the yield of hydrogen when contacting saidhydrocarbon feestream(s) with said cracking catalyst alone undercatalytic reaction conditions. More preferably, the yield of hydrogen isat least 25% less, more preferably at 50% less, even more preferably atleast 75%, more preferably, at least 90%, and most preferably greaterthan 99% less than the yield of hydrogen when contacting saidhydrocarbon feedstream(s) with said cracking catalyst alone undercatalytic reaction conditions.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

[0039] Unless otherwise stated, all percentages, parts, ratios, etc.,are by weight.

[0040] Unless otherwise stated, certain terms used herein shall have thefollowing meaning:

[0041] “paraffins” shall mean compounds having no carbon- carbon doublebonds and either the formula C_(n)H_(2n+2) or C_(n)H_(2n), where n is aninteger.

[0042] “naphthenes” shall mean compounds having no carbon-carbon doublebonds and the formula C_(n)H_(2n), where n is an integer.

[0043] “paraffinic feedstream” shall mean hydrocarbon feedstreamcontaining some amount of paraffins but no olefins.

[0044] “olefins” shall mean non-aromatic hydrocarbons having one or morecarbon-carbon double bonds.

[0045] “light olefins” shall mean ethylene, propylene, and, optionally,butylenes.

[0046] “light paraffins” shall mean methane, ethane, propane, and,optionally, butanes.

[0047] “catalyst to oil ratio” shall mean the relative amount ofcatalyst to hydrocarbon by weight.

[0048] “aromatics” shall mean compounds having one or more than onebenzene ring.

[0049] “physical admixture” shall mean a combination of two or morecomponents obtained by mechanical (i.e., non-chemical) means.

[0050] “chemically bound” shall mean bound via atom to atom bonds.

[0051] “cracking/selective hydrogen combustion” shall mean both crackingreaction and selective hydrogen combustion reaction.

[0052] “cracking catalyst” shall broadly mean a catalyst or catalystscapable of promoting cracking reactions whether used as base catalyst(s)and/or additive catalyst(s).

[0053] “selective hydrogen combustion catalyst” shall broadly mean amaterial or materials capable of promoting or participating in aselective hydrogen combustion reaction, using either free oxygen orlattice oxygen.

[0054] “cracking/selective hydrogen combustion catalyst” shall mean acatalyst system comprised of a physical admixture of one or morecracking catalysts and one or more selective hydrogen combustioncatalysts, or one or more selective hydrogen combustion catalystschemically bound to one or more cracking catalysts.

[0055] “cracking” shall mean the reactions comprising breaking ofcarbon-carbon bonds and carbon-hydrogen bonds of at least some feedmolecules and the formation of product molecules that have no carbonatom and/or fewer carbon atoms than that of the feed molecules.

[0056] selective hydrogen combustion” shall mean reacting hydrogen withoxygen to form water or steam without substantially and simultaneouslyreacting hydrocarbons with oxygen to form carbon monoxide, carbondioxide, and/or oxygenated hydrocarbons.

[0057] “yield” shall mean weight of a product produced per unit weightof feed, expressed in terms of weight %.

[0058] “Group 3 elements” shall mean elements having atomic numbers of21, 39, 57 through 71, and 89 through 92.

[0059] Unless otherwise stated, a reference to an element, compound orcomponent includes the element, compound or component by itself, as wellas in combination with other elements, compounds or components, such asmixtures of compounds.

[0060] Further, when an amount, concentration, or other value orparameter is given as a list of upper preferable values and lowerpreferable values, this is to be understood as specifically disclosingall ranges formed from any pair of an upper preferred value and a lowerpreferred value, regardless of whether ranges are separately disclosed.

[0061] The particulars shown herein are by way of example and forpurposes of illustrative discussion of the embodiments of the presentinvention only and are presented in the cause of providing what isbelieved to be the most useful and readily understood description of theprinciples and conceptual aspects of the present invention. In thisregard, no attempt is made to show structural details of the presentinvention in more detail than is necessary for the fundamentalunderstanding of the present invention, the description making apparentto those skilled in the art how the several forms of the presentinvention may be embodied in practice.

[0062] The present invention relates to a catalyst system for treating ahydrocarbon feedstream. Such feedstream could comprise, by way ofnon-limiting example, hydrocarbonaceous oils boiling in the range ofabout 221° C. to about 566° C., such as gas oil, steam cracked gas oiland residues; heavy hydrocarbonaceous oils comprising materials boilingabove 566 C; heavy and reduced petroleum crude oil, petroleumatmospheric distillation bottom, petroleum vacuum distillation bottom,heating oil, pitch, asphalt, bitumen, other heavy hydrocarbon residues,tar sand oils, shale oil, liquid products derived from coal liquefactionprocesses, and mixtures therefore. Other non-limiting feedstream couldcomprise steam heating oil, jet fuel, diesel, kerosene, gasoline, cokernaphtha, steam cracked naphtha, catalytically cracked naphtha,hydrocrackate, reformate, raffinate reformate, Fischer-Tropsch liquids,Fischer-Tropsch gases, natural gasoline, distillate, virgin naphtha, C₅₊olefins (i.e., C₅ olefins and above), C₅₊ paraffins, ethane, propane,butanes, butenes and butadiene. The present invention is also useful forcatalytically cracking olefinic and paraffinic feeds. Non-limitingexamples of olefinic feeds are cat-cracked naptha, coker naptha, steamcracked gas oil, and olefinic Fischer-Tropsch liquids. Non-limitingexamples of paraffinic feeds are virgin naptha, natural gasoline,reformate and raffinate. Preferably, the hydrocarbon feedstreamcomprises at least one of paraffins, olefins, aromatics, naphthenes, andmixtures thereof, which produces light olefins, hydrogen, lightparaffins, gasoline, and optionally, cracked naphtha, cracked gas oil,tar and coke. Typically, the cracked products from processes inaccordance with the present invention comprise hydrogen, light olefins,light paraffins, and olefins and paraffins having more than five carbonatoms. Products can be liquid and/or gaseous.

[0063] The catalyst system of the present invention comprises (1) atleast one solid acid component, (2) at least one metal-based componentcomprised of two or more elements from Groups 4-15 of the Periodic Tableof the Elements and at least one of oxygen and sulfur, wherein theelements from Groups 4-15 and the at least one of oxygen and sulfur arechemically bound both within and between the groups and (3) at least oneof at least one support, at least one filler and at least one binder.

[0064] As noted, the elements from Groups 4-15 are chemically bound bothwithin and between the groups. For example, it would be within the scopeof the present invention for two or more elements from Group 4 to bechemically bound to each other, as well as, chemically bound to theelement(s), if any, from remaining Groups 5-15.

[0065] The solid acid component is described by the Br{acute over(ø)}nsted and Lewis definitions of any material capable of donating aproton or accepting an electron pair. This description can be found inK. Tanabe. Solid Acids and Bases: their catalytic properties. Tokyo:Kodansha Scientific, 1970, p. 1-2. This reference is incorporated hereinby reference in its entirety. The solid acid component can comprise atleast one of solid acid, supported acid, or mixtures thereof. The solidacid component can comprise nonporous, microporous, mesoporous,macroporous or as a mixture thereof. These porosity designations areIUPAC conventions and are defined in K. S. W. Sing, D. H. Everett, R. A.W. Haul L. Moscou, R. A. Pierotti, J. Rouquérol, T. Siemieniewska,Pure&Appl. Chem. 1995, 57(4), pp. 603-619, which is incorporated hereinby reference in its entirety.

[0066] Non-limiting examples of solid acid components are natural clayssuch as kaolinite, bentonite, attapulgite, montmorillonite, clarit,fuller's earth, cation exhange resins and SiO₂.Al₂O₃, B₂O₃.Al₂O₃,Cr₂O₃.Al₂O₃, MoO₃.Al₂O₃, ZrO₂.SiO₂, Ga₂O₃.SiO₂, BeO.SiO₂, MgO.SiO₂,CaO.SiO₂, SrO.SiO₂, Y₂O₃.SiO₂, La₂O₃.SiO₂, SnO.SiO₂, PbO.SiO₂, MoO₃.Fe₂(MoO₄) ₃, MgO.B₂O₃, TiO₂.ZnO, ZnO, Al₂O₃, TiO₂, CeO₂, As₂O₃, V₂O₅, SiO₂,Cr₂O₃, MoO₃, ZnS, CaS, CaSO₄, MnSO₄, NiSO₄, CuSO₄, CoSO₄, CdSO₄, SrSO₄,ZnSO₄, MgSO₄, FeSO₄, BaSO₄, KHSO₄, K₂SO₄, (NH₄) ₂SO₄, Al₂(SO₄)₃,Fe₂(SO₄)₃, Cr₂(SO₄)₃, Ca(NO₃)₂, Bi(NO₃), Zn(NO₃)₂, Fe(NO₃)₃, CaCO₃,BPO₄, FePO₄,CrPO₄, Ti₃(PO₄)₄, Zr₃(PO₄)₄, Cu₃(PO₄)₂, Ni₃(PO₄)₂, AlPO₄,Zn₃(PO₄)₂, Mg₃(PO₄)₂, AlCl₃, TiCl₃, CaCl₂, AgCl₂, CuCl, SnCl₂, CaF₂,BaF₂, AgClO₄, and Mg(ClO₄)₂. Depending on the synthesis conditions,these materials can be prepared as nonporous, microporous, mesoporous,or macroporuous, as defined in the reference cited above. Conditionsnecessary to these preparations are known to those of ordinary skill inthe art.

[0067] Non-limiting examples of solid acids can also include bothnatural and synthetic molecular sieves. Molecular sieves havesilicate-based structures (“zeolites”) and AlPO-based structures. Somezeolites are silicate-based materials which are comprised of a silicalattice and, optionally, alumina combined with exchangeable cations suchas alkali or alkaline earth metal ions. For example, faujasites,mordenites and pentasils are non-limiting illustrative examples of suchsilicate-based zeolites. Silicate-based zeolites are made of alternatingSiO₂ and MO_(x) tetrahedral, where in the formula M is an elementselected from Groups 1 through 16 of the Periodic Table (new IUPAC).These types of zeolites have 8-, 10- or 12- membered ring zeolites, suchas Y, beta, ZSM-5, ZSM-22, ZSM-48 and ZSM-57.

[0068] Other silicate-based materials suitable for use in practicing thepresent invention include zeolite bound zeolites as described in WO97/45387, incorporated herein by reference in its entirety. Thesematerials comprise first crystals of an acidic intermediate pore sizefirst zeolite and a binder comprising second crystals of a secondzeolite. Unlike zeolites bound with amorphous material such as silica oralumina to enhance the mechanical strength of the zeolite, the zeolitebound zeolite catalyst does not contain significant amounts ofnon-zeolitic binders.

[0069] The first zeolite used in the zeolite bound zeolite catalyst isan intermediate pore size zeolite. Intermediate pore size zeolites havea pore size of from about 5 to about 7 Å and include, for example, AEL,MFI, MEL, MFS, MEI, MTW, EUO, MTT, HEU, FER, and TON structure typezeolites. These zeolites are described in Atlas of Zeolite StructureTypes, eds. W. H. Meier and D. H. Olson, Butterworth-Heineman, ThirdEdition, 1992, which is incorporated herein by reference in itsentirety. Non-limiting, illustrative examples of specific intermediatepore size zeolites are ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-34,ZSM-35, ZSM-38, ZSM-48, ZSM-50 AND ZSM-57. Preferred first zeolites aregalliumsilicate zeolites having an MFI structure and alumiminosilicatezeolites having an MFR structure.

[0070] The second zeolite used in the zeolite bound zeolite structurewill usually have an intermediate pore size (e.g., about 5.0 to about5.5 Å) and have less activity than the first zeolite. Preferably, thesecond zeolite will be substantially non-acidic and will have the samestructure type as the first zeolite. The preferred second zeolites arealuminosilicate zeolites having a silica to alumina mole ratio greaterthan 100 such as low acidity ZSM-5. If the second zeolite is analuminosilicate zeolite, the second zeolite will generally have a silicato alumina mole ratio greater than 100:1, e.g., 500:1; 1,000:1, etc.,and in some applications will contain no more than trace amounts ofalumina. The second zeolite can also be silicalite, i.e., a MFI typesubstantially free of alumina, or silicalite 2, a MEL type substantiallyfree of alumina. The second zeolite is usually present in the zeolitebound zeolite catalyst in an amount in the range of from about 10% to60% by weight based on the weight of the first zeolite and, morepreferably, from about 20% to about 50% by weight.

[0071] The second zeolite crystals preferably have a smaller size thanthe first zeolite crystals and more preferably will have an averageparticle size from about 0.1 to about 0.5 microns. The second zeolitecrystals, in addition to binding the first zeolite particles andmaximizing the performance of the catalyst will preferably intergrow andform an overgrowth which coats or partially coats the first zeolitecrystals. Preferably, the crystals will be resistant to attrition.

[0072] The zeolite bound zeolite catalyst is preferably prepared by athree step procedure. The first step involves the synthesis of the firstzeolite crystals prior to converting it to the zeolite bound zeolitecatalyst. Next, a silica-bound aluminosilicate zeolite can be preparedpreferably by mixing a mixture comprising the aluminosilicate crystals,a silica gel or sol, water and optionally an extrusion aid and,optionally, a metal component until a homogeneous composition in theform of an extrudable paste develops. The final step is the conversionof the silica present in the silica-bound catalyst to a second zeolitewhich serves to bind the first zeolite crystals together.

[0073] It is to be understood that the above description of zeolitebound zeolites can be equally applied to non-zeolitic molecular sieves(i.e., AlPO's).

[0074] Other molecular sieve materials suitable for this inventioninclude aluminophosphate-based materials. Aluminophosphate-basedmaterials are made of alternating AlO4 and PO4 tetrahedra. Members ofthis family have 8- (e.g., AlPO₄-12, -17, -21, -25, -34, -42, etc.) 10-(e.g., AlPO₄-11, 41, etc.), or 12-(AIPO₄-5, -31 etc.) membered oxygenring channels. Although AlPO₄s are neutral, substitution of Al and/or Pby cations with lower charge introduces a negative charge in theframework, which is countered by cations imparting acidity.

[0075] By turn, substitution of silicon for P and/or a P-Al pair turnsthe neutral binary composition (i.e., Al, P) into a series ofacidic-ternary-composition (Si, Al, P) based SAPO materials, such asSAPO-5, -11, -14, -17, -18, -20, -31, -34, -41, -46, etc. Acidic ternarycompositions can also be created by substituting divalent metal ions foraluminum, generating the MeAPO materials. Me is a metal ion which can beselected from the group consisting of, but not limited to Mg, Co, Fe, Znand the like. Acidic materials such as MgAPO (magnesium substituted),CoAPO (cobalt substituted), FeAPO (iron substituted), MnAPO (manganesesubstituted) ZnAPO (zinc substituted) etc. belong to this category.Substitution can also create acidic quaternary-composition basedmaterials such as the MeAPSO series, including FeAPSO (Fe, Al, P, andSi), MgAPSO (Mg, Al, P, Si), MnAPSO, CoAPSO, ZNAPSO (Zn, Al, P, Si),etc. Other substituted aluminophosphate-based materials include ElAPOand ElAPSO (where El=B, As, Be, Ga, Ge, Li, Ti, etc.). As mentionedabove, these materials have the appropriate acidic strength forreactions such as cracking. The more preferred aluminophosphate-basedmaterials include 10- and 12-membered ring materials (SAPO-11, -31, -41;MeAPO-11, -31, -41; MeAPSO-11, -31, 41; ElAPO-11, -31, -41; ElAPSO-11,-31, -41, etc.) which have significant olefin selectivity due to theirchannel structure.

[0076] Supported acid materials are either crystalline or amorphousmaterials, which may or may not be themselves acidic, modified toincrease the acid sites on the surface. Non-limiting, illustrativeexamples are H₂SO₄, H₃PO₄, H₃BO₃, CH₂(COOH)₂, mounted on silica, quartz,sand, alumina or diatomaceous earth, as well as heteropoly acids mountedon silica, quartz, sand, alumina or diatomaceous earth. Non-limiting,illustrative examples of crystalline supported acid materials areacid-treated molecular sieves, sulfated zirconia, tungstated zirconia,phosphated zirconia and phosphated niobia.

[0077] Although the term“zeolites” includes materials containing silicaand optionally, alumina, it is recognized that the silica and aluminaportions may be replaced in whole or in part with other oxides. Forexample, germanium oxide, tin oxide, phosphorus oxide, and mixturesthereof can replace the silica portion. Boron, oxide, iron oxide,gallium oxide, indium oxide, and mixtures thereof can replace thealumina portion. Accordingly, “zeolite” as used herein, shall mean notonly materials containing silicon and, optionally, aluminum atoms in thecrystalline lattice structure thereof, but also materials which containsuitable replacement atoms for such silicon and aluminum, such asgallosilicates, borosilicates, ferrosilicates, and the like.

[0078] Besides encompassing the materials discussed above, “zeolites”also encompasses aluminophosphate-based materials.

[0079] Mesoporous solid acids can be ordered and non-ordered.Non-limiting examples of ordered mesoporous materials include pillaredlayered clays (PILC's), MCM-41 and MCM-48. Non-limiting examples ofnon-ordered mesoporous materials include silica and titania-basedxerogels and aerogels.

[0080] The solid acid component can also be conventional FCC catalystincluding catalysts containing large-pore zeolite Y, modified zeolite Y,zeolite beta, and mixtures thereof, and catalysts containing a mixtureof zeolite Y or modified zeolite Y and a medium-pore, shape-selectivemolecular sieve species such as ZSM-5 or modified ZSM-5, or a mixture ofan amorphous acidic material and ZSM-5 or modified ZSM-5. Such catalystsare described in U.S. Pat. No. 5,318,692, incorporated by referenceherein. The zeolite portion of the FCC catalyst particle will typicallycontain from about 5 wt. % to 95 wt. % zeolite-Y (or alternatively theamorphous acidic material) and the balance of the zeolite portion beingZSM-5. Useful medium-pore, shape-selective molecular sieves includezeolites such as ZSM-5, which is described in U.S. Pat. Nos. 3,702,886and 3,770,614. ZSM-11 is described in U.S. Pat. No. 3,709,979; ZSM-12 inU.S. Pat. No. 3,832,449; ZSM-21 and ZSM-38 in U.S. Pat. No. 3,948,758;ZSM-23 in U.S. Pat. No. 4,076,842; and ZSM-35 in U.S. Pat. No.4,016,245. All of the above patents are incorporated herein byreference.

[0081] The large pore and shape selective zeolites may include“crystalline admixtures” which are thought to be the result of faultsoccurring within the crystal or crystalline area during the synthesis ofthe zeolites. Examples of crystalline admixtures of ZSM-5 and ZSM-11 aredisclosed in U.S. Pat. No. 4,229,424 which is incorporated herein byreference. The crystalline admixtures are themselves medium pore, i.e.,shape selective, size zeolites and are not to be confused with physicaladmixtures of zeolites in which distinct crystals of crystallites ofdifferent zeolites are physically present in the same catalyst compositeor hydrothermal reaction mixtures.

[0082] The conventional FCC catalyst may contain other reactive ornon-reactive components, such catalysts are described in European patentEP0600686B 1, incorporated by reference herein.

[0083] The metal-based component of the catalyst system in accordancewith the present invention is comprised of at least one metal-basedcomponent comprised of two or more elements from Groups 4-15 of thePeriodic Table of the Elements and at least one of oxygen and sulfur. Itis intended that reference to an element from each of the noted Groupswould include mixtures of elements from the respective groups. Forexample, reference to two or more element from Groups 4-15 includes amixture of elements from Groups 4 and 15 of the Periodic Table.

[0084] This metal-based component can adopt a perovskite (ABO₃) crystalstructure, where A and B are two distinct metal sites. Each metal sitecan comprise one or more metal cations from Group 1-15 of the PeriodicTable of Elements. The crystal structure can be significantly distortedfrom the idealized cubic, perovskite structure depending on the choiceof metals at A and B sites and/or due to the formation of oxygenvacancies upon reduction.

[0085] The metal-based component could be prepared, by way ofnon-limiting example, by combining salts or chalcogenides (compounds ofthe Group 16 elements) containing the desired parts through such meansas evaporation or precipitation, followed by calcination. The solid acidcomponent is then physically mixed or chemically reacted with themetal-based component and, optionally, combined with the binder to formcatalyst particles.

[0086] The preparation of the metal-based component and solid-acidcomponent are known to those of ordinary skill in the art. Themetal-based component can be obtained through chemical means, such asthe combination of metal salts and/or chalcogenides, in solution orslurry, followed by removal of the solvent or mother liquor viaevaporation or filtration and drying. The metal-based component can thenbe ground and calcined. The solid acid and metal-based components can bephysically admixed by mechanical mixing.

[0087] The elements from Groups 4-15 can be any two or more elementsfrom Groups 4-15 of the Periodic Table of the Elements. Preferably, theelements from Groups 4-15 are two or more of titanium, vanadium,chromium, manganese, iron, cobalt, nickel, copper, zinc, boron,aluminum, phosphorous, gallium, germanium, zirconium, niobium,molybdenum, ruthenium, rhodium, palladium, silver, indium, tin,antimony, hafnium, tungsten, rhenium, iridium, platinum, gold, lead andbismuth.

[0088] The remaining component (2) of the catalyst system in accordanceinvention can be at least one of sulfur and oxygen. Oxygen is preferred.

[0089] The solid acid component and the metal-based component of thecatalyst system in accordance with the present invention are chemicallybound. The chemically bound materials can then be subjected to thetreatment of a matrix component. The matrix component serves severalpurposes. It can bind the solid acid component and the metal-basedcomponent to form catalyst particles. It can serve as a diffusion mediumfor the transport of feed and product molecules. It can also act as afiller to moderate the catalyst activity. In addition, the matrix canhelp heat transfer or serve as metal sinks.

[0090] Examples of typical matrix materials include amorphous compoundssuch as silica, alumina, silica-alumina, silica-magnesia, titania,zirconia, and mixtures thereof. It is also preferred that separatealumina phases be incorporated into the inorganic oxide matrix. Speciesof aluminum oxyhydroxides-γ-alumina, boehmite, diaspore, andtransitional aluminas such as α-alumina, β-alumina, γ-alumina,δ-alumina, ε-alumina, κ-alumina, and ρ-alumina can be employed.Preferably, the alumina species is an aluminum trihydroxide such asgibbsite, bayerite, nordstrandite, or doyelite. The matrix material mayalso contain phosphorous or aluminum phosphate. The matrix material mayalso contain clays such as halloysite, kaolinite, bentonite,attapulgite, montmorillonite, clarit, fuller's earth, diatomaceousearth, and mixture thereof. The weight ratio of the solid acid componentand the metal-based component to the inorganic oxide matrix componentcan be about 100:1 to 1:100.

[0091] In another aspect of the present invention, the solid acidcomponent and the metal-based component of catalysts in accordance withthe present invention may be treated separately with a matrix component.The matrix component for the solid acid component can be the same as ordifferent from that for the metal-based component. One of the purposesof the treatment is to form particles of the solid acid component andparticles of the metal-based component so that the components are hardenough to survive interparticle and reactor wall collisions. The matrixcomponent may be made according to conventional methods from aninorganic oxide sol or gel, which is dried to “glue” the catalystparticle's components together. The matrix component can becatalytically inactive and comprises oxides of silicon, aluminum, andmixtures thereof. It is also preferred that separate alumina phases beincorporated into the inorganic oxide matrix. Species of aluminumoxyhydroxides-γ-alumina, boehmite, diaspore, and transitional aluminassuch as α-alumina, β-alumina, γ-alumina, δ-alumina, ε-alumina,κ-alumina, and ρ-alumina can be employed. Preferably, the aluminaspecies is an aluminum trihydroxide such as gibbsite, bayerite,nordstrandite, or doyelite. The matrix material may also containphosphorous or aluminum phosphate. The matrix material may also containclays such as kaolinite, bentonite, attapulgite, montmorillonite,clarit, fuller's earth, diatomaceous earth, and mixture thereof.

[0092] The weight ratio of the solid acid component to the matrixcomponent can be about 100:1 to 1:100. The weight ratio of themetal-based component to the matrix component can be about 100:1 to1:100

[0093] The solid-acid component particles and the metal-based componentparticles may be mixed to form a uniform catalyst system in the reactoror be packed in series to form a staged catalyst system in either asingle reactor or two or more staged reactors.

[0094] The catalyst system of the present invention is multifunctionalin that it both cracks a hydrocarbon feedstream and selectively combuststhe hydrogen produced from the cracking reaction. The solid acidcomponent of the catalyst system performs the cracking function and themetal-based component of the catalyst system performs the selectivehydrogen combustion function. The catalyst system is particularlywell-suited for cracking hydrocarbons to light olefins and gasoline.Conventional catalytic cracking generates hydrogen amongst other crackedproducts, which makes products recovery more difficult and costly. Thecatalyst system of the present invention can perform hydrocarboncracking without a substantial co-production of hydrogen therebyreducing the investment and operating costs and/or creating moreequipment volume for higher production capacity.

[0095] In accordance with the present invention, a catalyst systemcomprises a hydrocarbon cracking component and a selective hydrogencombustion component, which catalyst system, upon contact with ahydrocarbon feedstream, simultaneously cracks the hydrocarbon andselectively combusts the hydrogen produced from the cracking reaction.It is preferred that selective hydrogen combustion is conducted via ananaerobic mechanism which is related to the use of lattice oxygen fromthe selective hydrogen combustion component to promote selectivehydrogen combustion.

[0096] Selective hydrogen combustion could also help supply the heatrequired for hydrocarbon cracking. The combustion of hydrogen is highlyexothermic and, therefore, would be an ideal internal source of heatsupply. This could reduce or even eliminate the need for external heat.

[0097] Thus, in accordance with the present invention, a catalyticcracking process comprises contacting a hydrocarbon feedstream with acatalyst system comprising a cracking/selective hydrogen combustioncatalyst under suitable catalytic cracking/selective hydrogen combustionconditions to produce olefin, gasoline and other cracked products,wherein the catalytic cracking is conducted in a reduction of addedheat. “Reduction of added heat” is meant that less than 98% of the totalrequired heat input is added. More preferably, less than 95% of thetotal required heat input is added. Most preferably, less than 90% ofthe total required heat input is added. Since cracking reactions areendothermic, the required heat input is simply the overall enthalpy ofthe reaction. Thus, it is within the skill of one of ordinary skill inthe art to calculate the required heat input.

[0098] In accordance with the present invention, a free-oxygencontaining gas such as air or pure oxygen can be used as the source ofoxygen for the selective hydrogen combustion reaction. The free-oxygencontaining gas can be co-fed into the reaction vessel(s) with thehydrocarbon feedstream. Preferably, the lattice oxygen in themetal-based component of the catalyst system is used as the source ofoxygen for the selective hydrogen combustion reaction (anaerobichydrogen combustion). Higher selective hydrogen combustion selectivityand less COX by-product are achievable using this approach as comparedto co-feeding oxygen to the reactor. Using continuous catalystregeneration technology would overcome the potential problem related tolattice oxygen being quickly consumed with resultant loss of catalystactivity.

[0099] The inventive process can be performed using any known reactor.By way of non-limiting, illustrative example, fixed-bed reactors withcatalyst regeneration, moving bed reactors with catalyst regenerationsuch as the continuous catalyst regeneration reactor (also known asCCR), fluidized-bed processes such as a riser reactor with catalystregeneration and the like would be suitable. A non-limiting illustrativeexample of a suitable fixed-bed catalyst regeneration system isillustrated in U.S. Pat. No. 5,059,738 to Beech, Jr. et al, which isincorporated herein by reference in its entirety. A non-limitingillustrative example of a suitable continuous catalyst regenerationmoving bed reactor is illustrated in U.S. Pat. No. 5,935,415 to Haizmannet al, which is incorporated herein by reference in its entirety. Apreferred reactor system would be a downer-regenerator or ariser-regenerator system as described below for illustration purposesonly. A riser-regenerator system that would be suitable for use inpracticing the inventive process is disclosed in U.S. Pat. No.5,002,653, which is incorporated herein by reference in its entirety.

[0100] In a riser-regenerator system, pre-heated hydrocarbon feed iscontacted with catalyst in a feed riser line wherein the reactionprimarily takes place. The temperature and pressure for theriser/reactor can be in the range of 300-800° C. and 0.1-10 atmospheres,respectively. The catalyst to hydrocarbon feed ratio, weight basis, canbe in the range of 0.01 to 1000. The residence time in the reaction zonecan be in the range of 0.01 second to 10 hours. As the reactionsprogress, the catalyst system is progressively deactivated due to anumber of reasons including the consumption of lattice oxygen and theformation of coke on the catalyst surface. The catalyst system andhydrocarbon vapors are separated mechanically and hydrocarbons remainingon the catalyst are removed by steam stripping before the catalystsystem enters a catalyst regenerator. The hydrocarbon vapors are takenoverhead to a series of fractionation towers for product separation.Spent catalyst system is reactivated in the regenerator by burning offcoke deposits with air. The coke burn also serves as an oxidationtreatment to replenish the catalyst system's lattice oxygen consumed inthe reactor. The temperature and pressure for the regenerator can be inthe range of 300-800° C.and 0.1-10 atmospheres, respectively. Asrequired, a small amount of fresh make-up catalyst can be added to thereactor.

[0101] The cracking process of the present invention may also beperformed in one or more conventional FCC process units underconventional FCC conditions in the presence of the catalyst system ofthis invention. Each unit comprises a riser reactor having a reactionzone, a stripping zone, a catalyst regeneration zone, and at least onefractionation zone. The feed is conducted to the riser reactor where itis injected into the reaction zone wherein the heavy feed contacts aflowing source of hot, regenerated catalyst. The hot catalyst vaporizesand cracks the feed and selectively combusts the resultant hydrogen at atemperature from about 475° C. to about 650° C., preferably from about500° C. to about 600° C. The cracking reaction deposits carbonaceoushydrocarbons, or coke, on the catalyst system and the selective hydrogencombustion reaction depletes the lattice oxygen, thereby deactivatingthe catalyst system. The cracked products may be separated from thedeactivated catalyst system and a portion of the cracked products may befed to a fractionator. The fractionator separates at least a naphthafraction from the cracked products.

[0102] The deactivated catalyst system flows through the stripping zonewhere volatiles are stripped from the catalyst particles with astripping material such as steam. The stripping may be performed underlow severity conditions in order to retain absorbed hydrocarbons forheat balance. The stripped catalyst is then conducted to theregeneration zone where it is regenerated by burning coke on thecatalyst system and oxidizing the oxygen-depleted metal-based catalystcomponent in the presence of an oxygen containing gas, preferably air.Decoking and oxidation restore catalyst activity and simultaneouslyheats the catalyst system to, e.g., 650° C. to 800° C. The hot catalystis then recycled to the riser reactor at a point near or just upstreamof the second reaction zone. Flue gas formed by burning coke in theregenerator may be treated for removal of particulates and forconversion of carbon monoxide, after which the flue gas is normallydischarged into the atmosphere.

[0103] The feed may be cracked in the reaction zone under conventionalFCC conditions in the presence of the catalyst system of this invention.Preferred process conditions in the reaction zone include temperaturesfrom about 475° C. to about 650° C., preferably from about 500° C. to600° C.; hydrocarbon partial pressures from about 0.5 to 3.0atmospheres, preferably from about 1.0 to 2.5 atmospheres; and acatalyst to feed (wt/wt) ratio from about 1 to 30, preferably from about3 to 15; where catalyst weight is total weight of the catalystcomposite. Though not required, it is also preferred that steam beconcurrently introduced with the feed into the reaction zone, with thesteam comprising up to about 15 wt. %, and preferably ranging from about1 wt. % to about 5 wt. % of the feed. Also, it is preferred that thefeed's residence time in the reaction zone be less than about 100seconds, for example from about 0.01 to 60 seconds, preferably from 0.1to 30 seconds.

[0104] In accordance with the present invention, the weight ratio ofsolid acid component to the total weight of metal-based component isfrom 1000:1 to 1:1000. More preferably, the ratio is from 500:1 to1:500. Most preferably, the ratio is from 100:1 to 1:100.

EXAMPLES

[0105] The invention is illustrated in the following non-limitingexamples, which are provided for the purpose of representation, and arenot to be construed as limiting the scope of the invention. All partsand percentages in the examples are by weight unless indicatedotherwise.

Example 1

[0106] This example illustrates the hydrogen yield during hydrocarboncracking using a conventional zeolitic catalyst, without the addition ofselective hydrogen combustion (SHC) catalyst. 4.0 grams of OlefinsMax(Grace Davison Division of W.R. Grace & Co.) were pelletized, crushedand screened to 30-50 mesh powder. It was then steamed at 700° C. for 2hours. 1.0 gram of steamed OlefinsMax was then physically mixed with 2.5grams of SiC (16-25 mesh), and loaded into a fixed-bed reactor fortesting. The catalyst was heated to 540° C. in a helium stream at a flowrate of 105 cc/min (cubic centimeters per minute) and a pressure of 2-4psig. The temperature was allowed to stabilize for 30 minutes prior tothe addition of hydrocarbon feed. The feed consisted of 0.384 cc/min of2-methylpentane or Light Virgin Naphtha (LVN) and 0.025 cc/min of liquidwater. Following the introduction of hydrocarbon feed, product sampleswere collected every 30 seconds for a total time-period of 3.5 minutesusing a multi-port, gas-sampling valve. The product was analyzed using agas chromatograph equipped with flame ionization and pulsed dischargedetectors. Table 1 shows the hydrogen and combined yield of C₁-C₄products at various conversions of 2-methylpentane. When LVN was used asfeed, similar hydrogen and C₁-C₄ yields were obtained when compared atthe same feed conversion. A small CO_(x) yield (typically, <0.1 wt %)was observed due to background contamination and/or hydrocarbonoxidation during post-reaction sampling/analysis. TABLE 12-Methylpentane Conversion C₁-C₄ Yield (wt %) Hydrogen Yield (wt %) 39.233.3 0.230 ± 0.012 21.1 18.6 0.131 ± 0.007 8.1 6.7 0.044 ± 0.002

Example 2

[0107] This example illustrates the preparation and performance ofselective hydrogen combustion (SHC) catalyst for reducing the hydrogenyield in the product, while minimizing non-selective hydrocarbonoxidation. In_(0.9)Zn_(0.1)MnO₃ catalyst was prepared byco-precipitation of metal salts using an organic base and a carbonateprecursor. Solution A was prepared by dissolving 6.742 grams of indium(III) nitrate hydrate (Alfa Aesar, Ward Hill, Mass.), 0.516 grams ofzinc acetate dihydrate (Aldrich Chemical Company, Milwaukee, Wis.) and6.688 grams of manganese (II) nitrate hydrate (Aldrich Chemical Company,Milwaukee, Wis.) in 117 grams of deionized water. Solution B wasprepared by dissolving 14.6 sodium bicarbonate (Mallinckrodt Baker Inc.,Paris, Ky.), 43.7 grams of tetraethylammonium hydroxide, 35 wt %solution (Alfa Aesar, Ward Hill, Mass.) in 693 grams of deionized water.Solution A was slowed poured into a well-stirred solution B, resultingin precipitate formation. After aging the suspension for 1 hour, theparticles were recovered by centrifugation at 1500-2000 rpm. Theprecipitate was then resuspended in 250 mL of ethanol (Alfa Aesar, WardHill, Mass.) followed by centrifugation to remove water, impuritycations/anions. The precipitate was dried in air at 25° C., ground to afine powder using a mortar and pestle, and calcined to 800° C. for 2hours in air. The sample was pelletized, crushed, and screened to 30-50mesh prior to SHC testing.

[0108] 1.0 grams of steamed OlefinsMax (prepared as described inExample 1) was physically mixed with 0.5 grams of SHC catalyst and 2.0gram of SiC, and loaded into a fixed bed reactor. All other testingconditions were kept the same as in Example 1. Table 2 shows the resultsof the SHC test. TABLE 2 SHC Catalyst In_(0.9)Zn_(0.1)MnO₃ % Conversion8.9 C1-C4 Yield (wt %) 7.1 H₂ Yield (wt %) 0.010 % H₂ Conversion 78CO_(x) Yield (wt %) 0.012 % H₂ Selectivity 97

[0109] The data in Table 2 demonstrates that significant reductions inhydrogen yield can be achieved through the addition of SHC catalyst.Compared to Example 1, there is a 78 percent reduction in hydrogen yieldat similar hydrocarbon conversion and C1-C4 yields. Moreover, the SHCcatalyst exhibits a very high selectivity of 97 percent for hydrogencombustion, resulting in virtually no CO_(x) formation throughnon-selective hydrocarbon activation.

Example 3

[0110] This example illustrates the preparation and performance ofselective hydrogen combustion (SHC) catalyst for reducing the hydrogenyield in the product, while minimizing non-selective hydrocarbonoxidation. In_(0.95)Cu_(0.05)MnO₃ catalyst was prepared byco-precipitation of metal salts using an organic base and a carbonateprecursor. Solution A was prepared by dissolving 7.038 grams of indiumnitrate hydrate (Alfa Aesar, Ward Hill, Mass.), 0.281 grams of copper(II) nitrate hydrate (Alfa Aesar, Ward Hill, Mass.), and 6.614 grams ofmanganese (II) nitrate hydrate (Aldrich Chemical Company, Milwaukee,Wis.) in 116 grams of deionized water. Solution B was prepared bydissolving 14.5 grams of sodium bicarbonate (Mallinckrodt Baker Inc.,Paris, Ky.), 43.6 grams of tetraethylammonium hydroxide, 35 wt %solution (Alfa Aesar, Ward Hill, Mass.) in 691 grams of deionized water.Solution A was slowed poured into a well-stirred solution B, resultingin precipitate formation. After aging the suspension for 1 hour, theparticles were recovered by centrifugation at 1500-2000 rpm. Theprecipitate was then resuspended in 250 mL of ethanol (Alfa Aesar, WardHill, Mass.) followed by centrifugation to remove water, impuritycations/anions. This washing step was repeated to ensure completeremoval of impurities. The precipitate was dried in air at 25° C.,ground to a fine powder using a mortar and pestle, and calcined to 800°C. for 2 hours in air. The sample was pelletized, crushed, and screenedto 30-50 mesh prior to SHC testing.

[0111] 1.0 grams of steamed OlefinsMax (prepared as described inExample 1) was physically mixed with 0.5 grams of SHC catalyst and 2.0gram of SiC, and loaded into a fixed bed reactor. All other testingconditions were kept the same as in Example 1. Table 3 shows the resultsof the SHC test. TABLE 3 SHC Catalyst In_(0.95)Cu_(0.05)MnO₃ %Conversion 8.1 C1-C4 Yield (wt %) 6.1 H₂ Yield (wt %) 0.0038 % H₂Conversion 91 CO_(x) Yield (wt %) 0.158 % H₂ Selectivity 71

[0112] The data in Table 3 demonstrates that significant reductions inhydrogen yield can be achieved through the addition of SHC catalyst.Compared to Example 1, there is a 91 percent reduction in hydrogen yieldat similar hydrocarbon conversion and C1-C4 yields. Moreover, the SHCcatalyst exhibits a high selectivity of 71 percent for hydrogencombustion, resulting in minimal COx formation through non-selectivehydrocarbon activation.

We claim:
 1. A catalyst system comprising (1) at least one solid acidcomponent, (2) at least one metal-based component comprised of two ormore elements from Groups 4-15 of the Periodic Table of the Elements andat least one of oxygen and sulfur, wherein the elements from Groups 4-15and the at least one of oxygen and sulfur are chemically bound bothwithin and between the groups and (3) at least one of at least onesupport, at least one filler and at least one binder.
 2. The catalystsystem of claim 1, wherein the solid acid component is in physicaladmixture with the metal-based component.
 3. The catalyst system ofclaim 1, wherein the solid acid component and the metal-base componentare chemically bound.
 4. The catalyst system of claim 2, wherein thesolid acid component is at least one of one or more amorphous solidacids, one or more crystalline solid acids, one or more supported acidsand mixtures thereof.
 5. The catalyst system of claim 4, wherein the atleast one of oxygen and sulfur is oxygen.
 6. The catalyst system ofclaim 1, wherein the one or more elements from Groups 4-15 are titanium,vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc,boron, aluminum, phosphorous, gallium, germanium, zirconium, niobium,molybdenum, ruthenium, rhodium, palladium, silver, indium, tin,antimony, hafnium, tungsten, rhenium, iridium, platinum, gold, lead andbismuth.
 7. The catalyst system of claim 1, wherein the metal-basedcomponent comprises at least one perovskite crystal structure.
 8. Thecatalyst system of claim 6, wherein the metal-based component comprisesat least one perovskite crystal structure.
 9. The catalyst system ofclaim 1, wherein the solid acid component comprises at least onemolecular sieve.
 10. The catalyst system of claim 9, wherein themolecular sieve comprises at least one zeolite.
 11. The catalyst systemof claim 1, wherein the weight ratio of solid acid component to thetotal weight of metal-based component is 1:1000 to 1000:1.
 12. Thecatalyst system of claim 11, wherein the weight ratio of solid acidcomponent to the total weight of metal-based component is 1:500 to500:1.
 13. The catalyst system of claim 12, wherein the weight ratio ofsolid acid component to the total weight of metal-based component is1:100 to 100:1.
 14. The catalyst system of claim 10, wherein the zeolitecomprises at least one of MFI and faujasite.
 15. The catalyst system ofclaim 10, wherein the zeolite comprises at least one of ZSM-5 and Yzeolite.
 16. The catalyst system of claim 1, wherein the solid acidcomponent further comprises at least one of at least one support, atleast one filler and at least one binder.
 17. The catalyst system ofclaim 1, wherein the metal-based component further comprises at leastone of at least one support, at least one filler and at least onebinder.
 18. The catalyst system of claim 16, wherein the metal-basedcomponent further comprises at least one of at least one support, atleast one filler and at least one binder.
 19. The catalyst system ofclaim 9, wherein the molecular sieve comprises at least one ofcrystalline silicates, crystalline substituted silicates, crystallinealuminosilicates, crystalline substituted aluminosilicates, crystallinealuminophosphates, crystalline substituted aluminophosphates,zeolite-bound-zeolite, having 8- or greater-than-8 membered oxygen ringsin framework structures.
 20. The catalyst system of claim 19, whereincrystalline substituted aluminophosphates comprise SAPO, MeAPO, MeAPSO,ELAPO, and ELAPSO.
 21. A process for treating a hydrocarbon feedstreamcomprising simultaneously contacting the feedstream under crackingconditions with a catalyst system comprising (1) at least one solid acidcomponent, (2) at least one metal-based component comprised of two ormore elements from Groups 4-15 of the Periodic Table of the Elements andat least one of oxygen and sulfur, wherein the elements from Groups 4-15and the at least one of oxygen and sulfur are chemically bound bothwithin and between the groups and (3) at least one of at least onesupport, at least one filler and at least one binder.
 22. The process ofclaim 21, wherein the hydrocarbon feedstream is cracked and theresultant hydrogen simultaneously combusted.
 23. The process of claim22, wherein said hydrogen combustion comprises selective hydrogencombustion.
 24. The process of claim 22, wherein the selective hydrogencombustion is anaerobic selective hydrogen combustion without thefeeding of free-oxygen containing gas into the reactor.
 25. The processof claim 22, wherein the selective hydrogen combustion is conducted withthe feeding of free-oxygen containing gas into the reactor.
 26. Theprocess of claim 22, wherein the catalyst system is regeneratedperiodically.
 27. The process of claim 21, wherein the solid acidcomponent is at least one of one or more amorphous solid acids, one ormore crystalline solid acids, one or more supported acids and mixturesthereof.
 28. The process of claim 21, wherein the solid acid componentcomprises at least one molecular sieve.
 29. The process of claim 28,wherein the weight ratio of solid acid component to the total weight ofmetal-based component is 1:1000 to 1000:1.
 30. The process of claim 29,wherein the process temperature is from 300-800° C.
 31. The process ofclaim 30, wherein the process pressure is from 0.1 to 10 atmospheres.32. The process of claim 31, wherein the catalyst system to oil ratio isfrom 0.01 to
 1000. 33. The process of claim 32, wherein the residencetime is from 0.01 second to 10 hours.
 34. The process of claim 21, whichproduces liquid and gaseous hydrocarbons.
 35. The process of claim 21,wherein the acid component is at least one cracking catalyst and themetal-based component is at least one selective hydrogen combustioncatalyst.
 36. The process of claim 35, wherein the cracking catalyst isat least one of at least one fluid catalytic cracking base catalyst, atleast one fluid catalytic cracking additive catalyst, and mixturethereof.
 37. The process of claim 21, conducted in reduction of addedheat.
 38. The process of claim 21, wherein the yield of hydrogen is lessthan the yield of hydrogen when contacting said hydrocarbon feedstreamwith said solid acid component alone under said catalytic reactionconditions.
 39. The process of claim 38, wherein the yield of hydrogenis at least 10% less than the yield of hydrogen when contacting saidhydrocarbon feedstream(s) with said solid acid component alone undersaid catalytic reaction conditions.
 40. The process of claim 39, whereinthe yield of hydrogen is at least 25% less than the yield of hydrogenwhen contacting said hydrocarbon feedstream(s) with said solid acidcomponent alone under said catalytic reaction conditions.
 41. Theprocess of claim 40, wherein the yield of hydrogen is at least 50% lessthan the yield of hydrogen when contacting said hydrocarbonfeedstream(s) with said solid acid component alone under said catalyticreaction conditions.
 42. The process of claim 41, wherein the yield ofhydrogen is at least 75% less than the yield of hydrogen when contactingsaid hydrocarbon feedstream(s) with said solid acid component aloneunder said catalytic reaction conditions.
 43. The process of claim 42,wherein the yield of hydrogen is at least 90% less than the yield ofhydrogen when contacting said hydrocarbon feedstream(s) with said solidacid component alone under said catalytic reaction conditions.
 44. Theprocess of claim 43, wherein the yield of hydrogen is greater than 99%less than the yield of hydrogen when contacting said hydrocarbonfeedstream(s) with said solid acid component alone under said catalyticreaction conditions.
 45. The process of claim 22, wherein thehydrocarbon feedstream comprises at least one of gas oil, steam crackedgas oil and residues; heavy hydrocarbonaceous oils comprising materialsboiling above 566° C.; heavy and reduced petroleum crude oil, petroleumatmospheric distillation bottom, petroleum vacuum distillation bottom,heating oil, pitch, asphalt, bitumen, other heavy hydrocarbon residues,tar sand oils, shale oil, liquid products derived from coal liquefactionprocesses, steam heating oil, jet fuel, diesel, kerosene, gasoline,coker naphtha, steam cracked naphtha, catalytically cracked naphtha,hydrocrackate, reformate, raffinate reformate, Fischer-Tropsch liquids,Fischer-Tropsch gases, natural gasoline, distillate, virgin naphtha, C₅₊olefins, C₅₊ paraffins, ethane, propane, butanes, butenes and butadiene,olefinic and paraffinic feeds.
 46. The process of claim 45, wherein thefeedstream comprises at least one of paraffins, olefins, aromatics, andnaphthenes
 47. A process comprising: (a) charging at least onehydrocarbon feedstream to a fluid catalytic cracking reactor, (b)charging a hot fluidized cracking/selective hydrogen combustion catalystsystem from a catalyst regenerator to said fluid catalytic crackingreactor, said catalyst system comprising (1) at least one solid acidcomponent, (2) at least one metal-based component comprised of two ormore elements from Groups 4-15 of the Periodic Table of the Elements andat least one of oxygen and sulfur, wherein the elements from Groups 4-15and the at least one of oxygen and sulfur are chemically bound bothwithin and between the groups and (3) at least one of at least onesupport, at least one filler and at least one binder, (c) catalyticallycracking said feedstream(s) and combusting resultant hydrogen at300-800° C. to produce a stream of cracked products and uncracked feedand a spent catalyst system comprising said fluid catalytic crackingcatalyst and said selective hydrogen combustion catalyst which aredischarged from said reactor, (d) separating a phase rich in saidcracked products and uncracked feed from a phase rich in said spentcatalyst system, (e) stripping said spent catalyst system at strippingconditions to produce a stripped catalyst phase, (f) decoking andoxidizing said stripped catalyst phase in a catalyst regenerator atcatalyst regeneration conditions to produce said hot fluidizedcracking/selective hydrogen combustion catalyst system, which isrecycled to the said reactor, and (g) separating and recovering saidcracked products and uncracked feed.
 48. The process of claim 47,wherein the yield of hydrogen is less than the yield of hydrogen whencontacting said hydrocarbon feedstream(s) with said fluid catalyticcracking catalyst component alone under said catalytic reactionconditions.
 49. The process of claim 47, wherein the cracking/selectivehydrogen combustion catalyst system comprises a physical mixture of atleast one fluid catalytic cracking catalyst component and at least oneselective hydrogen combustion catalyst component.
 50. The process ofclaim 47, wherein the catalytic cracking catalyst component comprises atleast one of a fluid catalytic cracking base catalyst component and afluid catalytic cracking additive catalyst component.
 51. The process ofclaim 50, wherein the fluid catalytic cracking additive catalystcomponent is at least one of octane-boosting additives, metalpassivation additives, CO oxidation additives, coke oxidation additives,SOx reduction additives, NOx reduction additives, and mixtures thereof.52. The process of claim 47, wherein the cracking/selective hydrogencombustion catalyst system comprises at least one fluid catalyticcracking catalyst component chemically bound to at least one selectivehydrogen combustion catalyst component.
 53. The process of claim 52,wherein the fluid catalytic cracking catalyst component comprises atleast one of a fluid catalytic cracking base catalyst component and afluid catalytic cracking additive catalyst component.
 54. The process ofclaim 53, wherein the additive catalyst component is at least one ofoctane-boosting additives, metal passivation additives, CO oxidationadditives, coke oxidation additives, SOx reduction additives, NOxreduction additives, and mixtures thereof.